Methoxyiminoacetic acid derivative and agricultural/horticultural fungicide containing the same as active ingredient

ABSTRACT

A methoxyiminoacetic acid derivative represented by the following formula (I): ##STR1## wherein X represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; A represents a methoxy group or a methylamino group; when A is a methoxy group, B represents --O--CO-- or --N=C(R 1 )-- and when A is a methylamino group, B represents --O--CR 1  R 2  --, wherein R 1  and R 2  independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group; and Ar represents an optionally substituted aryl group or an optionally substituted heteroaryl group, and an agricultural/horticultural fungicide containing the same as an active ingredient.

FIELD OF THE INVENTION

This invention relates to a novel methoxyiminoacetic acid derivative and an agricultural/horticultural fungicide containing the same as an active ingredient.

BACKGROUND OF THE INVENTION

It has been known that certain methoxyiminoacetic acid derivatives have biological activities including fungicidal activities. For example, a compound of the formula: ##STR2## is described in EP 398692. Further a compound of the formula: ##STR3## is described in WO92/13830 and EP 463488. Furthermore, a compound of the formula: ##STR4## is described in EP 499823. Also, a compound of the formula: ##STR5## is described in EP515901.

However, these compounds are not always satisfactory as an agricultural/horticultural fungicide, as will be shown in Test Examples hereinafter.

SUMMARY OF THE INVENTION

Under these circumstances, the present inventors have paid their attention to these methoxyiminoacetic acid derivatives and conducted extensive studies thereon. As a result, it has successfully been found out that a methoxyiminoacetic acid derivative having a specific structure has a potent fungicidal activity as well as an excellent systemic and residual activity for plants, thus completing the present invention.

Accordingly, the gist of the present invention resides in a methoxyiminoacetic acid derivative represented by the following formula (I): ##STR6## wherein X represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; A represents a methoxy group or a methylamino group; when A is a methoxy group, B represents --O--CO-- or --N=C(R¹)-- and when A is a methylamino group, B represents --O--CR¹ R² --, wherein R¹ and R² independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group or a trifluoromethyl group; and Ar represents an optionally substituted aryl group or an optionally substituted heteroaryl group, and an agricultural/horticultural fungicide containing the same as an active ingredient.

DETAILED DESCRIPTION OF THE INVENTION

Now, the present invention will be described in detail.

The methoxyiminoacetic acid derivative of the present invention is the one represented by the above formula (I). In the above formula (I), X represents a hydrogen atom; a halogen atom (for example, fluorine, chlorine, bromine); an alkyl group having 1 to 4 carbon atoms (for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl); or an alkoxy group having 1 to 4 carbon atoms (for example, methoxy, ethoxy, iso-propoxy, n-butoxy). It preferably represents a hydrogen atom or a halogen atom, still preferably a hydrogen atom.

A represents a methoxy group or a methylamino group. It preferably represents a methylamino group.

When A is a methoxy group, B represents --O--CO-- or --N=C(R¹)--. When A is a methylamino group, B represents --O--CR¹ R² --. R¹ and R² independently represent a hydrogen atom; an alkyl group having 1 to 4 carbon atoms (for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl); a cyano group; or a trifluoromethyl group. It preferably represents a hydrogen atom, a cyano group or a methyl group.

Ar represents an aryl group (for example phenyl, naphthyl) which may be optionally substituted by the following groups; or a heteroaryl group (for example, pyridyl, thienyl, thiazolyl) which may be optionally substituted by the following groups. It preferably represents a phenyl group which may be optionally substituted by the following groups, a naphthyl group, a thienyl group which may be optionally substituted by the following groups, or a thiazolyl group which may be optionally substituted by the following groups.

Examples of the substituents for the above-mentioned aryl group include a cyano group; a halogen atom (for example, fluorine, chlorine, bromine); an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl); an alkenyl group having 2 to 4 carbon atoms (for example, ethenyl, propenyl) optionally substituted by a halogen atom; a haloalkyl group having 1 to 4 carbon atoms (for example, trifluoromethyl, difluoromethyl, trichloromethyl, dichlorodifluoroethyl); an alkoxy group having 1 to 6 carbon atoms (for example, methoxy, ethoxy, iso-propoxy, n-butoxy) optionally substituted by a halogen atom or a cycloalkyl group having 3 to 6 carbon atoms; an alkylcarbonyloxy group having 1 to 7 carbon atoms (for example, acetoxy, propionyloxy, pivaloyloxy) optionally substituted by a halogen atom; an acylamino group having 1 to 7 carbon atoms (for example, acetoamino, propionylamino) optionally substituted by a halogen atom; an alkylthio group having 1 to 6 carbon atoms (for example, methylthio, ethylthio, iso-propylthio, n-butylthio) optionally substituted by a halogen atom; an aryl group (for example, phenyl) optionally substituted by an alkyl group having 1 to 4 carbon atoms or a halogen atom; an aryloxy group (for example, phenoxy) optionally substituted by an alkyl group having 1 to 4 carbon atoms or a halogen atom; an alkylsulfonyloxy group having 1 to 6 carbon atoms (for example, methanesulfonyloxy or ethanesulfonyloxy) optionally substituted by a halogen atom; an alkenyloxy group having 2 to 6 carbon atoms (for example, propenyloxy) optionally substituted by a halogen atom; and an alkynyloxy group having 2 to 6 carbon atoms (for example, propargyloxy). From among these substituents, those adjacent to each other may be combined together to give, for example, a methylenedioxy or ethylenedioxy group and form a fused ring together with an aryl group. The number of substituents is from 1 to 5, preferably from 1 to 2. When Ar has two or more substituents, they may be the same or different each other. Preferable examples of substituents for an aryl group include an alkyl group having 1 to 4 carbon atoms, a halogen atom, an alkoxy group having 1 to 4 carbon atoms which may be optionally substituted by a halogen atom (preferably fluorine), an acylamino group having 1 to 4 carbon atoms which may be optionally substituted by a halogen atom (preferably fluorine), an alkylthio group having 1 to 3 carbon atoms, an alkylsulfonyloxy group having 1 to 3 carbon atoms which may be optionally substituted by a halogen atom (preferably fluorine) and a trifluoromethyl group.

Examples of the substituents for the above-mentioned heteroaryl group include a cyano group; a halogen atom (for example, fluorine, chlorine, bromine); an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl); a haloalkyl group having 1 to 4 carbon atoms (for example, trifluoromethyl, difluoromethyl, trichloromethyl, dichlorodifluoroethyl); and an alkoxy group having 1 to 6 carbon atoms (for example, methoxy, ethoxy, iso-propoxy, n-butoxy) optionally substituted by a halogen atom or a cycloalkyl group having 3 to 6 carbon atoms. The number of substituents, which may be the same or different each other, is from 1 to 2. Among these substituents, an alkyl group having 1 to 4 carbon atoms, a halogen atom and a trifluoromethyl group may be cited as preferable ones.

The compounds of the present invention are each a novel one and can be prepared, for example, in accordance with the following reaction scheme: ##STR7## [wherein X, R¹, R² and Ar are as defined in the above formula (I)].

The compounds represented by the above formulae (II) and I-a) can be prepared by, respectively, reacting the benzaldehyde derivatives of the above formulae (III) and (V) with a hydroxylamine hydrochloride and reacting the oxime derivatives (IV) and (VI) thus obtained with the corresponding benzyl halide derivative or benzoyl halide derivative in the presence of an appropriate base in an inert solvent (for example, diethyl ether, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, methylene chloride, dichloroethane).

Examples of the base to be used in the above reaction include an alkali metal hydride (for example, sodium hydride); an alkali metal alcoholate (for example, sodium methylate); an alkali metal carbonate (for example, potassium carbonate); an alkali metal hydroxide (for example, potassium hydroxide); a tertiary amine (for example, N-methylmorpholine, triethylamine); and an aromatic base (for example, pyridine, picoline).

In some cases, the compound of the above formula (II) can be directly obtained by reacting the benzaldehyde derivative (III) with o-substituted hydroxylamine in an inert solvent such as an alcohol.

The compound of the above formula (I-b) can be obtained by reacting the benzaldehyde derivative represented by the above formula (V) with the corresponding hydrazone derivative in an inert solvent such as an alcohol.

The above-mentioned compounds of formulae (III) and (V) as starting materials can be produced in accordance with the method described in EP398693, EP499823 or the like.

In some cases, the compound of the above formula (II) can be prepared in accordance with the following reaction scheme: ##STR8## [wherein R¹, R² and Ar are as defined in the above formula (I) and R³ represents an alkyl group having 1 to 10 carbon atoms].

The compounds of the above formula (II) can be obtained by reacting an ester derivative (VII) with methylamine in an inert solvent such as an alcohol.

The compounds of the above formulae (II), (I-a) and (I-b) each exists as isomers at the methoxyimino moiety. Each isomer can be separated each other from the mixture of isomers which is obtained usually, by a conventional manner such as column chromatography. Each of E-, X-mixture or Z-isomer can be converted to the E-isomer which shows high activities, by treating with an acid (for example, hydrochloric acid, sulfuric acid, methanesulfonic acid) in an alcohol solvent (for example, methanol, ethanol).

The compounds of the present invention thus obtained are each a novel one having an excellent fungicidal activity. They exert excellent preventive effects on various phytopathogenic fungi, which makes them useful as an agricultural/horticultural fungicide.

For example, these compounds exert high activity on rice blast (Pyricularia oryzae), rice sheath blight (Rhizoctonia solani), wheat powdery mildew (Erysiphe graminis f. sp. hodei), various leaf rusts of wheat and barley (e.g. Puccinia recondita), gray mold of vegetables and fruit trees (Botrytis cinerea) and late blight of various crops ((Phytophthora infestance). Further, they have prolonged residual activity and excellent systemic action in plants, which makes them highly useful as an agricultural/horticultural fungicide.

When the compound of the present invention is to be used as an agricultural/horticultural fungicide, it may be applied as such. However, it is preferable to formulate said compound into, for example, emulsifiable concentrate, wettable powder, dust or granules by blending with adjuvants in a conventional manner to thereby ensure the effective dispersion of the active ingredient at the application.

When the agricultural/horticultural fungicide according to the present invention is to be formulated into an emulsifiable concentrate, 10 to 80 parts by weight (hereinafter referred to as "parts") (preferably 10 to 70 parts) of the compound of the present invention, 10 to 90 parts (preferably 20 to 80 parts) of a solvent and 3 to 20 parts (preferably 5 to 15 parts) of a surfactant are mixed together at an appropriate ratio. At the usage, the obtained mixture is diluted with water to a definite concentration and applied by, for example, spraying.

When the agricultural/horticultural fungicide of the present invention is to be used as a wettable powder, 5 to 80 parts (preferably 10 to 70 parts) of the compound of the present invention, 10 to 90 parts (preferably 20 to 80 parts) of a filler and 1 to 20 parts (preferably 3 to 15 parts) of a surfactant are mixed together at an appropriate ratio. At the usage, the obtained mixture is diluted with, for example, water to a definite concentration and applied, similar to the case of the emulsifiable concentrate.

When the agricultural/horticultural fungicide of the present invention is to be used as a dust, 0.1 to 10 parts (preferably 1 to 5 parts) of the compound of the present invention is uniformly mixed with 90 to 99.9 parts (preferably 95 to 99 parts) of a filler (for example, kaolin, bentonite, talc).

The agricultural/horticultural fungicide of the present invention may further contain other active ingredients such as bactericides, insecticides and miticides, so long as the effects of the active ingredient of the present invention are not deteriorated thereby.

The agricultural/horticultural fungicide of the present invention can be suitably used either in foliar application or in submerged application. In the case of foliar application, the agricultural/horticultural fungicide is usually formulated into an emulsifiable concentrate or a wettable powder and diluted with water so as to give a concentration of the active ingredient of from 10 to 1,000 ppm. then it is applied at a ratio of 100 to 5000 1 per 1 ha.

To further illustrate the present invention in greater detail, the following Examples will be given. However, it is to be understood that the present invention is not restricted thereto but various changes may be restored within the scope thereof.

SYNTHESIS EXAMPLE 1

Synthesis of N-methyl-2-[2-{3-(trifluoromethyl)benzyloxyiminomethyl}phenyl]-2-methoxyiminoacetamide (compound No. 1 in Table 1):

To a solution of 0.53 g of methyl 2-[2-{3-(trifluoromethyl)benzyloxyiminomethyl}phenyl]-2-methoxyiminoacetate in 5 ml of methanol, was added 5 ml of a 40% methylamine/methanol solution and the mixture was stirred at room temperature overnight. After the completion of the reaction, the solvent was distilled off and the residue was recrystallized from ethyl acetate/hexane (1:9). Thus 0.56 g of the title compound was obtained (quantitative yield).

The compound No. 2 in Table 1 and the compound No. 78 in Table 2 were synthesized by repeating the above-mentioned procedure except altering the starting material.

SYNTHESIS EXAMPLE 2

Synthesis of N-methyl-2-{2-(3-chlorobenzyloxyiminomethyl)-phenyl}-2-methoxyiminoacetamide (compound No. 3 in Table 1):

To a solution of 1 g (4.26 mmol) of N-methyl-2-{2-(hydroxyiminomethyl)phenyl}-2-methoxyiminoacetamide and 0.62 g (4.5 mmol) of potassium carbonate in 10 ml of DMF, was added 0.69 g (4.29 mmol) of 3-chlorobenzyl chloride and the mixture was stirred under heating at 110° C. for 3 hours. After cooling, the reaction mixture was poured into water, extracted with ethyl acetate, successively washed with water and a saturated sodium chloride solution and dried over anhydrous sodium sulfate. After concentration in vacuo, the residue was chromatographed over SiO₂ to give 0.9 g of the title compound (yield: 58.8%).

The compounds No. 4 to No. 8 and No. 11 to No. 14 in Table 1 were synthesized by repeating the above-mentioned procedure except altering the starting material.

SYNTHESIS EXAMPLE 3

Synthesis of N-methyl-2-[2-{α-methyl-4-(trifluoromethyl)-benzyloxyiminomethyl}phenyl]-2-methoxyiminoacetamide (compound No. 24 in Table 1):

To a solution of 0.6 g (2.7 mmol) of N-methyl-2-(2-formylphenyl)-2-methoxyiminoacetamide in 7 ml of methanol, was added 0.42 g (3.0 mmol) of α-methyl-4-(trifluoromethyl)-benzyloxyamine and the mixture was allowed to stand at room temperature overnight. After the reaction mixture was concentrated in vacuo, the residue was chromatographed over SiO₂ to yield 0.89 g of the title compound (yield:95%).

The compounds Nos. 16-18, 20, 21, 23 ,25, 27-29, 31, 32, 35, 38-40, 42, 44, 46, 47, 49-68 and 72 in Table 1 and the compounds Nos. 76, 77 and 79-83 in Table 2 were synthesized by repeating the above-mentioned procedure except altering the starting material.

SYNTHESIS EXAMPLE 4

Synthesis of methyl 2-[2-{4-(3-trifluoromethylphenyl)-2,3-diaza-1,3-pentadienyl}phenyl]-2-methoxyiminoacetate (compound No. 88 in Table 3):

A mixture comprising 1.5 g (6.75 mmol) of methyl 2-(2-formylphenyl)-2-methoxyiminoacetate, 1.37 g (6.75 mmol) of m-trifluoromethylacetophenone hydrazone and 7.5 ml of ethanol was heated under reflex for 3 hours. After vacuum concentration, the residue was chromatographed over SiO₂ to give 2.48 g of the title compound (yield: 86.6%).

The compounds No. 86, No. 87, No. 89 and No. 90 in Table 3 were synthesized by repeating the above-mentioned procedure except altering the starting material.

SYNTHESIS EXAMPLE 5

Synthesis of methyl 2-[2-{4-(trifluoromethyl)benzyloxyiminomethyl}phenyl]-2-methoxyiminoacetate compound No. 91 in Table 3):

To a mixture comprising 0.60 g (2.53 mmol) of methyl 2-{2-(hydroxyiminomethyl)phenyl}-2-methoxyiminoacetate, 1 ml of triethylamine and 5 ml of dichloromethane, was added 0.80 g (3.8 mmol) of p-trifluoromethylbenzoic acid chloride under ice cooling. After stirring at room temperature for 12 hours, the reaction mixture was poured into water and extracted with ethyl acetate. Then it was successively washed with eater and a saturated sodium chloride solution and dried over anhydrous sodium sulfate. After vacuum concentration, the residue was chromatographed over SiO₂ to give 0.31 g of the title compound (yield: 30.0%).

                  TABLE 1                                                          ______________________________________                                          ##STR9##                                                                      Com-                                                                           pound                                                                          No.   R.sup.1                                                                               R.sup.2                                                                               X   (Y).sub.n   Property                                   ______________________________________                                          1    H      H      H   3-CF.sub.3  m.p. 93-97° C.                       2    H      H      H   4-CF.sub.3  nD 1.5505/25° C.                     3    H      H      H   3-Cl        m.p. 90-93° C.                       4    H      H      H   4-Cl        m.p. 119-123° C.                     5    H      H      H   3-CH.sub.3  m.p. 90-93° C.                       6    H      H      H   4-CH.sub.3  m.p. 148-150° C.                     7    H      H      H   2,5-(CH.sub.3).sub.2                                                                       m.p. 106.5-107° C.                   8    H      H      H   3-OCH.sub.3 viscous                                     9    H      H      H   4-OCH.sub.3 viscous                                    10    H      H      H   3-OCF.sub.3 viscous                                    11    H      H      H   4-OCF.sub.3 m.p. 96-97° C.                      12    H      H      H   2,5-Cl.sub.2                                                                               m.p.                                                                           148.5-150.5° C.                     13    H      H      H   3,5-(CF.sub.3).sub.2                                                                       m.p. 102.5-105° C.                  14    CH.sub.3                                                                              H      H   --          m.p.                                                                           107.5-110.2° C.                     15    CH.sub.3                                                                              H      H   2-Cl        viscous                                    16    CH.sub.3                                                                              H      H   3-Cl        m.p. 82.5-83° C.                    17    CH.sub.3                                                                              H      H   4-Cl        m.p. 87.5-90.5° C.                  18    CH.sub.3                                                                              H      H   4-Cl        viscous                                    19    CH.sub.3                                                                              H      H   3-Br        viscous                                    20    CH.sub.3                                                                              H      H   4-Br        amorphous solid                            21    CH.sub.3                                                                              H      H   3,4-Cl.sub.2                                                                               m.p.                                                                           110.9-111.7° C.                     22    CH.sub.3                                                                              H      H   2,5-Cl.sub.2                                                                               viscous                                    23    CH.sub.3                                                                              H      H   3-CF.sub.3  m.p. 88.5-89° C.                    24    CH.sub.3                                                                              H      H   4-CF.sub.3  m.p. 70.5-71.5° C.                  25    CH.sub.3                                                                              H      H   4-CF.sub.3  viscous                                    26    CH.sub.3                                                                              H      H   2-CH.sub.3  viscous                                    27    CH.sub.3                                                                              H      H   3-CH.sub.3  viscous                                    28    CH.sub.3                                                                              H      H   4-CH.sub.3  viscous                                    29    CH.sub.3                                                                              H      H   2,4-(CH.sub.3).sub.2                                                                       viscous                                    30    CH.sub.3                                                                              H      H   2,5-(CH.sub.3).sub. 2                                                                      viscous                                    31    CH.sub.3                                                                              H      H   3,4-(CH.sub.3).sub.2                                                                       viscous                                    32    CH.sub.3                                                                              H      H   4-C.sub.2 H.sub.5                                                                          amorphous solid                            33    CH.sub.3                                                                              H      H   4-C.sub.3 H.sub.7 (n)                                                                      viscous                                    34    CH.sub.3                                                                              H      H   4-C.sub.3 H.sub.7 (iso)                                                                    viscous                                    35    CH.sub.3                                                                              H      H   4-C.sub.4 H.sub.9 (tert)                                                                   viscous                                    36    CH.sub.3                                                                              H      H   2-OCH.sub.3 viscous                                    37    CH.sub.3                                                                              H      H   3-OCH.sub.3 viscous                                    38    CH.sub.3                                                                              H      H   4-OCH.sub.3 amorphous solid                            39    CH.sub.3                                                                              H      H   4-OC.sub.2 H.sub.5                                                                         amorphous solid                            40    CH.sub.3                                                                              H      H   4-OC.sub.3 H.sub.7 (n)                                                                     amorphous solid                            41    CH.sub.3                                                                              H      H   3-OC.sub.3 H.sub.7 (iso)                                                                   amorphous solid                            42    CH.sub.3                                                                              H      H   4-OC.sub.3 H.sub.7 (iso)                                                                   amorphous solid                            43    CH.sub.3                                                                              H      H   3-propargyloxy                                                                             amorphous solid                            44    CH.sub.3                                                                              H      H   4-propargyloxy                                                                             amorphous solid                            45    CH.sub.3                                                                              H      H   4-OCH.sub.2 CHCCl.sub.2                                                                    viscous                                    46    CH.sub.3                                                                              H      H   3-OPh       amorphous solid                            47    CH.sub.3                                                                              H      H   4-OPh       amorphous solid                            48    CH.sub.3                                                                              H      H   4-cyclopropyl-                                                                             viscous                                                            methyloxy                                              49    CH.sub.3                                                                              H      H   3-OCF.sub.3 m.p. 82-83° C.                      50    CH.sub.3                                                                              H      H   4-OCF.sub.3 amorphous solid                            51    CH.sub.3                                                                              H      H   3-OCHF.sub.2                                                                               viscous                                    52    CH.sub.3                                                                              H      H   4-OCHF.sub.2                                                                               viscous                                    53    CH.sub.3                                                                              H      H   3-OCH.sub.2 CF.sub.3                                                                       viscous                                    54    CH.sub.3                                                                              H      H   4-OCH.sub.2 CF.sub.3                                                                       viscous                                    55    CH.sub.3                                                                              H      H   4-OCH.sub.2 CF.sub.2 CF.sub.3                                                              viscous                                    56    CH.sub.3                                                                              H      H   3-OSO.sub.2 CF.sub.3                                                                       viscous                                    57    CH.sub.3                                                                              H      H   4-OSO.sub.2 CF.sub.3                                                                       viscous                                    58    CH.sub.3                                                                              H      H   3-OSO.sub.2 C.sub.2 H.sub.5                                                                viscous                                    59    CH.sub.3                                                                              H      H   4-OSO.sub.2 C.sub.2 H.sub.5                                                                viscous                                    60    CH.sub.3                                                                              H      H   4-NHCOCF.sub.3                                                                             viscous                                    61    CH.sub.3                                                                              H      H   4-CN        m.p.                                                                           122.8-123.7° C.                     62    CH.sub.3                                                                              H      H   4-CN        amorphous solid                            63    CH.sub.3                                                                              H      H   4-Ph        m.p. 65-70.9° C.                    64    CH.sub.3                                                                              H      H   3-SCH.sub.3 viscous                                    65    CH.sub.3                                                                              H      H   4-SCH.sub.3 viscous                                    66    CH.sub.3                                                                              H      H   3-SC.sub.3 H.sub.7 (iso)                                                                   viscous                                    67    CH.sub.3                                                                              H      H   4-SC.sub.3 H.sub.7 (iso)                                                                   viscous                                    68    CN     H      H   4-CF.sub.3  viscous                                    69    C.sub.2 H.sub.5                                                                       CH.sub.3                                                                              H   4-Cl        viscous                                    70    C.sub.2 H.sub.5                                                                       H      H   4-OCOC.sub.2 H.sub.5                                                                       viscous                                    71    C.sub.2 H.sub.5                                                                       H      H   4-OCF.sub.3 viscous                                    72    CN     H      H   --          viscous                                    73    CF.sub.3                                                                              H      H   4-CF.sub.3  viscous                                    74    CH.sub.3                                                                              H      3-  --          viscous                                                        Cl                                                         75    CH.sub.3                                                                              H      3-  4-CF.sub.3  viscous                                                        Cl                                                         ______________________________________                                          *The compounds No. 18, No. 25 and No. 62 are respectively isomers of the       compounds No. 17, No. 24 and No. 61 at the benzyloxyimino moiety.              **Although E and Zisomers at the methoxyimino moiety exist, the propertie      of Eisomers alone are given in the above table.                          

                  TABLE 2                                                          ______________________________________                                          ##STR10##                                                                     Compound                                                                       No.     R.sup.1                                                                               R.sup.2                                                                               Ar           Property                                    ______________________________________                                         76      CH.sub.3                                                                              H      2-naphthyl   amorphous solid                             77      CH.sub.3                                                                              H      1-naphthyl   viscous                                     78      H      H      6-chloropyridine-2-                                                                         viscous                                                           yl                                                       79      CH.sub.3                                                                              H      6-trifluoromethyl-                                                                          viscous                                                           pyridine-2-yl                                            80      CH.sub.3                                                                              H      3,4-         amorphous solid                                                   methylenedioxyphenyl                                     81      CH.sub.3                                                                              H      3,4-         viscous                                                           ethylenedioxyphenyl                                      82      CH.sub.3                                                                              H      5-chloro-2-thienyl                                                                          viscous                                     83      CH.sub.3                                                                              H      2-chloro-4-  viscous                                                           methylthiazole-5-yl                                      84      CH.sub.3                                                                              CH.sub.3                                                                              2,4-         viscous                                                           dimethylthiazole-5-                                                            yl                                                       85      C.sub.2 H.sub.5                                                                       H      2-t-butylthiazole-5-                                                                        viscous                                                           yl                                                       ______________________________________                                          *Although E and Zisomers at the methoxyimino moiety exist, the properties      of the Eisomers alone are given in the above table.                      

                  TABLE 3                                                          ______________________________________                                          ##STR11##                                                                     Compound                                                                       No.        B           (Y).sub.n                                                                               Property                                       ______________________________________                                         86         NC(CH.sub.3)                                                                               3-CH.sub.3                                                                               97-104° C.                             87         NC(CH.sub.3)                                                                               3-Cl     117-118.5° C.                           88         NC(CH.sub.3)                                                                               3-CF.sub.3                                                                              138-138.5° C.                           89         NC(CH.sub.3)                                                                               4-Cl     129-132° C.                             90         NC(CH.sub.3)                                                                               4-CF.sub.3                                                                              141-144° C.                             91         OC(O)       4-CF.sub.3                                                                              nD 1.5474/25                                   ______________________________________                                          *Although E and Zisomers at the methoxyimino moiety exist, the properties      of the Eisomers alone are given in the above table.                      

¹ H-NMR data of the obtained compounds are as follows. [Table 1]

¹ H-NMR data of compound No. 1 (CDCl₃): 2.89 (3H, d), 3.89 (3H, s), 5.20 (2H, s), 6.73 (1H, brs), 7.18 (1H, dd), 7.39 (1H, dd), 7.42 (1H, d), 7.49 (1H,d) 7.55-7.60 (2H, m), 7.64 (1H, s), 7.76 (1H, dd), 7.97 (1H, s)

¹ H-NMR data of compound No. 2 (CDCl₃); 2.79 (3H, d), 3.85 (3H, s), 5.18 (2H, s), 6.95 (1H, br), 7.19 (1H, d), 7.32-7.40 (2H, m), 7.47 (2H, d), 7.59 (2H,d), 7.76 (1H, d), 8.03 (1H, s)

¹ H-NMR data of compound No. 3 (CDCl₃); 2.89 (3H, d), 3.90 (3H, s), 5.11 (2H, s), 6.71 (1H, brs), 7.18 (1H, dd), 7.24-7.30 (3H, m), 7.37 (1H, s), 7.39 (1H,dd), 7.41 (1H, dd), 7.74 (1H, dd), 7.96 (1H, s)

¹ H-NMR data of compound No. 4 (CDCl₃); 2.89 (3H, d), 3.90 (3H, s), 5.11 (2H, s), 6.69 (1H, brs), 7.17 (1H, dd), 7.32 (4H, s), 7.39 (1H, dd), 7.41 (1H, dd), 7.75 (1H, dd), 7.94 (1H, s)

¹ H-NMR data of compound No. 5 (CDCl₃); 2.35 (3H, s), 2.83 (3H, d), 3.87 (3H, s), 5.11 (2H, s), 6.71 (1H, brs), 7.11 (1H, d), 7.15-7.27 (4H, m), 7.36 (1H, dd), 7.39 (1H, dd), 7.76 (1H, dd), 7.95 (1H, s)

¹ H-NMR data of compound No. 6 (CDCl₃); 2.35 (3H, s), 2.88 (3H, d), 3.90 (3H, s), 5.11 (2H, s), 6.67 (1H, brs), 7.17 (2H, d), 7.18 (1H, dd), 7.28 (2H, d), 7.38 (1H, dd), 7.41 (1H, dd), 7.77 (1H, dd), 7.93 (1H, s)

¹ H-NMR data of compound No. 7 (CDCl₃); 2.33 (3H, s), 2.34 (3H, s), 2.88 (3H, d), 3.91 (3H, s), 5.15 (2H, s), 6.68 (1H, brs), 7.05 (1H, d), 7.08 (1H, d), 7.16 (1H, s), 7.18 (1H, dd), 7.39 (1H, dd), 7.42 (1H, dd), 7.80 (1H, dd), 7.94 (1H, s)

¹ H-NMR data of compound No. 8 (CDCl₃); 2.86 (3H, s), 3.81 (3H, s), 3.90 (3H, s), 5.15 (2H, s), 6.76 (1H, br), 6.87 (1H, d), 6.96 (1H, s), 6.98 (1H, d), 7.20 (1H, dd), 7.29 (1H, dd), 7.39 (1H, dd), 7.42 (1H, dd), 7.78 (1H, dd), 7.99 (1H, s)

¹ H-NMR data of compound No. 11 (CDCl₃); 2.88 (3H, d), 3.89 (3H, s), 5.14 (2H, s), 6.71 (1H, br), 7.16-7.24 (3H, m), 7.38-7.44 (4H, m), 7.76 (1H, dd), 7.95 (1H, s),

¹ H-NMR data of compound No. 12 (CDCl₃); 2.90 (3H, d), 3.92 (3H, s), 5.23 (2H, s), 6.75 (1H, brs), 7.19 (1H, dd), 7.22 (1H, dd), 7.30 (1H, d), 7.39-7.45 (3H, m), 7.75 (1H, dd), 8.01 (1H, s)

¹ H-NMR data of compound No. 13 (CDCl₃); 2.91 (3H, d), 3.89 (3H, s), 5.24 (2H, s), 6.77 (1H, br), 7.18 (1H, dd), 7.37-7.46 (2H, m), 7.76 (1H, dd), 7.83 (3H, s), 7.98 (1H, s)

¹ H-NMR data of compound No. 14 (CDCl₃); 1.58 (3H, d), 2.86 (3H, d), 3.87 (3H, s), 5.26 (1H, q), 6.56 (1H, br), 7.16 (1H, m), 7.3-7.4 (7H), 7.68 (1H, m), 7.96 (1H, s)

¹ H-NMR data of compound No. 16 (CDCl₃); 1.55 (3H, d), 2.87 (3H, d), 3.88 (3H, s), 5.22 (1H, q), 6.63 (1H, br), 7.15 (1H, dd), 7.19-7.28 (3H, m), 7.33 (1H, s), 7.36 (1H, dd), 7.39 (1H, dd), 7.67 (1H, dd), 7.96 (1H, s)

¹ H-NMR data of compound No. 17 (CDCl₃); 1.56 (3H, d), 2.83 (3H, d), 3.87 (3H, s), 5.26 (1H, q), 6.76 (1H, brs), 7.17 (1H, dd), 7.26-7.40 (6H, m), 7.70 (1H, dd), 7.98 (1H, s)

¹ H-NMR data of compound No. 18 (CDCl₃); 1.55 (3H, d), 2.90 (3H, d), 3.90 (3H, s), 5.25 (1H, q), 6.77 (1H, br), 7.2-8.3 (9H, m)

¹ H-NMR data of compound No. 20 (CDCl₃); 1.55 (3H, d), 2.88 (3H, d), 3.88 (3H, s), 5.22 (1H, q), 6.6 (1H, br), 7.16 (1H, m), 7.22 (2H, d), 7.38 (2H, m), 7.47 (2H, d), 7.68 (1H, m), 7.94 (1H, s)

¹ H-NMR data of compound No. 21 (CDCl₃); 1.54 (3H, d), 2.89 (3H, d), 3.89 (3H, s), 5.20 (1H, q), 6.68 (1H, br), 7.18 (2H, m), 7.4 (4H, m), 7.68 (1H, m), 7.95 (1H, s)

¹ H-NMR data of compound No. 23 (CDCl₃); 1.58 (3H, d), 2.88 (3H, d), 3.86 (3H, s), 5.30 (1H, q), 6.67 (1H, br), 7.15 (1H, dd), 7.35-7.55 (5H, m), 7.60 (1H, s), 7.68 (1H, dd), 7.96 (1H, s)

¹ H-NMR data of compound No. 24 (CDCl₃); 1.57 (3H, d), 2.87 (3H, d), 3.86 (3H, s), 5.31 (1H, q), 6.63 (1H, br), 7.15 (1H, dd), 7.35-7.40 (2H, m), 7.46 (2H, d), 7.60 (2H, d), 7.67 (1H, dd), 7.97 (1H, s)

¹ H-NMR data of compound No. 25 (CDCl₃); 1.56 (3H, d), 2.87 (3H, d), 3.88 (3H, s), 5.32 (1H, q), 6.82 (1H, br), 7.2-8.3 (9H, m),

¹ H-NMR data of compound No. 27 (CDCl₃); 1.59 (3H, d), 2.38 (3H, s), 2.85 (3H, d), 3.89 (3H, s), 5.26 (1H, q), 6.63 (1H, br), 7.08-7.30 (5H, m), 7.37 (1H, dd), 7.40 (1H, dd), 7.71 (1H, dd), 7.98 (1H, s)

¹ H-NMR data of compound No. 28 (CDCl₃); 1.56 (3H, d), 2.34 (3H, s), 2.86 (3H, d), 3.88 (3H, s), 5.23 (1H, q), 6.58 (1H, br), 7.15 (1H, dd), 7.16 (2H, d), 7.24 (2H, d), 7.36 (1H, dd), 7.39 (1H, dd), 7.68 (1H, dd), 7.94 (1H, s)

¹ H-NMR data of compound No. 29 (CDCl₃); 1.55 (3H, d), 2.30 (3H, s), 2.35 (3H, s), 2.86 (3H, d), 3.89 (3H, s), 5.47 (1H, q), 6.55 (1H, brs), 6.99 (1H, d), 7.02 (1H, d), 7.17 (1H, dd), 7.27 (1H, dd), 7.37 (2H, m), 7.70 (1H, dd), 7.94 (1H, s)

¹ H-NMR data of compound No. 31 (CDCl₃); 1.56 (3H, d), 2.25 (3H, s), 2.27 (3H, s), 2.86 (3H, d), 3.88 (3H, s), 5.20 (1H, q), 6.60 (1H, brs), 7.1-7.2 (4H, m), 7.37 (2H, m), 7.70 (1H, dd), 7.94 (1H, s)

¹ H-NMR data of compound No. 32 (CDCl₃); 1.24 (3H, t), 1.57 (3H, d), 2.64 (2H, q), 2.86 (3H, d), 3.87 (3H, s), 5.23 (1H, q), 6.56 (1H, br), 7.17 (1H, m), 7.18 (2H, d), 7.27 (2H, d), 7.37 (2H, m), 7.7 (1H, m), 7.95 (1H, s)

¹ H-NMR data of compound No. 35 (CDCl₃); 1.28 (9H, s), 1.58 (3H, d), 2.86 (3H, d), 3.87 (3H, s), 5.27 (1H, q), 6.6 (1H, br), 7.16 (1H, m), 7.29 (2H, d), 7.38 (4H, m), 7.7 (1H, m), 7.95 (1H, s)

¹ H-NMR data of compound No. 38 (CDCl₃); 1.57 (3H, d), 2.87 (3H, d), 3.81 (3H, s), 3.88 (3H, s), 5.22 (1H, q), 6.62 (1H, br), 6.90 (2H, d), 7.16 (1H, m), 7.30 (2H, d), 7.38 (2H, m), 7.69 (1H, m), 7.93 (1H, s)

¹ H-NMR data of compound No. 39 (CDCl₃); 1.41 (3H, t), 1.56 (3H, d), 2.87 (3H, d), 3.89 (3H, s), 4.02 (2H, q), 6.6 (1H, br), 6.88 (2H, d), 7.16 (1H, m), 7.3 (2H, d), 7.38 (2H, m), 7.7 (1H, m), 7.93 (1H, s)

¹ H-NMR data of compound No. 40 (CDCl₃); 1.03 (3H, t), 1.57 (3H, d), 1.8 (2H, q), 2.87 (3H, d), 3.89 (3H, s), 3.91 (2H, t), 5.21 (1H, q), 6.6 (1H, br), 6.9 (2H, d), 7.18 (1H, m), 7.3 (2H, d), 7.37 (2H, m), 7.7 (1H, m), 7.93 (1H, s)

¹ H-NMR data of compound No. 42 (CDCl₃); 1.33 (6H, d), 1.56 (3H, d), 2.87 (3H, d), 3.89 (3H, d), 4.52 (1H, m), 5.21 (1H, q), 6.62 (1H, br), 6.85 (2H, d), 7.16 (1H, m), 7.27 (2H, d), 7.38 (2H, m), 7.70 (1H, m), 7.93 (1H, s)

¹ H-NMR data of compound No. 44 (CDCl₃); 1.57 (3H, d), 2.50 (1H, t), 2.87 (3H, d), 3.88 (3H, s), 4.69 (2H, d), 5.21 (1H, q), 6.61 (1H, br), 6.97 (2H, d), 7.16 (1H, m), 7.30 (2H, d), 7.38 (2H, m), 7.70 (1H, m), 7.93 (1H, s)

¹ H-NMR data of compound No. 49 (CDCl₃); 1.56 (3H, d), 2.88 (3H, d), 3.87 (3H, s), 5.57 (1H, d), 6.67 (1H, br), 7.13 (1H, d), 7.15 (1H, dd), 7.20 (1H, s), 7.28 (1H, d), 7.34-7.42 (3H, m), 7.68 (1H, dd), 7.96 (2H, s)

¹ H-NMR data of compound No. 50 (CDCl₃); 1.57 (3H, d), 2.88 (3H, d), 3.87 (3H, s), 5.28 (1H, q), 6.64 (1H, br), 7.16 (2H, dd), 7.19 (2H, d), 7.38 (4H, m), 7.68 (1H, dd), 7.95 (1H, s)

¹ H-NMR data of compound No. 54 (CDCl₃); 1.56 (3H, d), 2.88 (3H, d), 3.89 (3H, s), 4.35 (2H, q), 5.25 (1H, q), 6.64 (1H, br), 6.93 (2H, d), 7.17 (1H, dd), 7.32 (2H, d), 7.38 (2H, m), 7.70 (1H, dd), 7.93 (1H, s)

¹ H-NMR data of compound No. 55 (CDCl₃); 1.57 (3H, d), 2.86 (3H, d), 3.89 (3H, s), 4.42 (2H, t), 5.23 (1H, q), 6.68 (1H, br), 6.93 (2H, d), 7.16 (1H, dd), 7.32 (2H, d), 7.38 (2H, m), 7.7 (1H, dd), 7.93 (1H, s)

¹ H-NMR data of compound No. 56 (CDCl₃); 1.56 (3H, d), 2.86 (3H, d), 3.86 (3H, s), 5.29 (1H, q), 6.80 (1H, br), 7.14-7.21 (2H, m), 7.27 (1H, s), 7.33-7.45 (4H, m), 7.68 (1H, dd), 7.98 (1H, s)

¹ H-NMR data of compound No. 58 (CDCl₃); 1.47 (3H, t), 1.56 (3H, d), 2.86 (3H, d), 3.24 (2H, q), 3.84 (3H, s), 5.27 (1H, q), 6.77 (1H, br), 7.14 (1H, dd), 7.18 (1H, d), 7.25 (1H, s), 7.29 (1H, d), 7.33-7.41 (3H, m), 7.66 (1H, dd), 7.96 (1H, s)

¹ H-NMR data of compound No. 61 (CDCl₃); 1.56 (3H, d), 2.89 (3H, d), 3.89 (3H, s), 5.30 (1H, q), 6.66 (1H, br), 7.15 (1H, m), 7.38 (2H, m), 7.42 (2H, d), 7.64 (2H, d), 7.68 (1H, m), 7.96 (1H, m)

¹ H-NMR data of compound No. 62 (CDCl₃); 1.54 (3H, d), 2.87 (3H, d), 3.87 (3H, s), 5.22 (1H, q), 6.64 (1H, br), 7.16 (1H, m), 7.22 (2H, d), 7.37 (2H, m), 7.47 (2H, d), 7.66 (1H, m), 7.94 (1H, s)

¹ H-NMR data of compound No. 63 (CDCl₃); 1.62 (3H, d), 2.85 (3H, d), 3.87 (3H, s), 5.34 (1H, q), 6.60 (1H, br), 7.18 (1H, m), 7.3-7.7 (12H), 7.98 (1H, s) [Table 2]

¹ H-NMR data of compound No. 76 (CDCl₃); 1.66 (3H, d), 2.78 (3H, d), 3.81 (3H, s), 5.42 (1H, q), 6.5 (1H, br), 7.15 (1H, m), 7.36 (2H, m), 7.5 (3H, m), 7.66 (1H, m), 7.8 (4H, m), 8.01 (1H, s)

¹ H-NMR data of compound No. 78 (CDCl₃); 2.88 (3H, d), 3.88 (3H, s), 5.23 (2H, s), 6.82 (1H, br), 7.18 (1H, dd), 7.24 (1H, d), 7.33 (1H, d), 7.39 (1H, dd), 7.42 (1H, dd), 7.66 (1H, dd), 7.70 (1H, dd), 8.04 (1H, s)

¹ H-NMR data of compound No. 80 (CDCl₃); 1.54 (3H, d), 2.89 (3H, d), 3.89 (3H, s), 5.18 (1H, q), 5.94 (2H, s), 6.65 (1H, br), 6.7-6.9 (3H, m), 7.16 (1H, m), 7.38 (2H, m), 7.69 (1H, m), 7.93 (1H, s)

¹ H-NMR data of compound No. 81 (CDCl₃); 1.54 (3H, d), 2.89 (3H, d), 3.89 (3H, s), 4.25 (4H, s), 5.15 (1H, q), 6.66 (1H, br), 6.84 (2H, d), 6.88 (1H, d), 7.15 (1H, m), 7.38 (2H, m), 7.70 (1H, m), 7.92 (1H, s)

¹ H-NMR data of compound No. 82 (CDCl₃); 1.64 (3H, d), 2.91 (3H, d), 3.92 (3H, s), 5.36 (1H, q), 6.75 (1H, br), 6.78 (2H, m), 7.19 (1H, m), 7.4 (2H, m), 7.75 (1H, m), 7.90 (1H, s) [Table 3]

¹ H-NMR data of compound No. 86 (CDCl₃); 2.41 (3H, s), 2.46 (3H, s), 3.82 (3H, s), 4.03 (3H, s), 7.23-7.35 (3H, m), 7.48-7.54 (2H, m), 7.66 (1H, d), 7.73 (1H, s), 7.87 (1H, dd), 8.37 (1H, s)

¹ H-NMR data of compound No. 87 (CDCl₃); 2.44 (3H, s), 3.81 (3H, s), 4.03 (3H, s), 7.26 (1H, dd), 7.31-7.43 (2H, m), 7.48-7.54 (2H, m), 7.76 (1H, d), 7.86 (1H, dd), 7.91 (1H, s), 8.37 (1H, s)

¹ H-NMR data of compound No. 88 (CDCl₃); 2.49 (3H, s), 3.82 (3H, s), 4.03 (3H, s), 7.27 (1H, dd), 7.51 (2H, dd), 7.54 (1H, d), 7.67 (1H, d), 7.87 (1H, dd), 8.06 (1H, d), 8.19 (1H, s), 8.39 (1H, s)

¹ H-NMR data of compound No. 91 (CDCl₃); 3.92 (3H, s), 4.06 (3H, s), 7.29 (1H, d), 7.49-7.62 (2H, m), 7.77 (2H, d), 8.10 (1H, d), 8.23 (2H, d), 8.38 (1H, s)

FORMULATION EXAMPLE 1

A wettable powder was obtained by uniformly pulverizing and mixing 20 parts of the compound No. 2 given in Table 1, 75 parts of diatomaceous earth and 5 parts of a surfactant comprising alkyl benzenesulfonate as a main component.

FORMULATION EXAMPLE 2

An emulsifiable concentrate was obtained by mixing and dissolving 30 parts of the compound No. 3 given in Table 1, 15 parts of "Sorpol®" 3005X (a nonionic surfactant/anionic surfactant mixture manufactured by Toho Chemical Industry Co., Ltd.) 25 parts of xylene and 30 parts of dimethylformamide.

To clarify the usefulness of the compounds of the present invention as an agricultural/horticultural fungicide, the following Test Examples will be given.

TEST EXAMPLE 1

Preventive activity on wheat powdery mildew

A wettable powder prepared in the same manner as described in Formulation Example 1 was diluted with water to a definite concentration and then applied by foliar application on what plants (var. Norin No. 61) at the 1 to 2 leaf stage grown in pots of 6 cm in diameter at a ratio of 10 ml/pot. After air-drying the chemical solution, a spore suspension of Erysiphe graminis (a pathogen of wheat powdary mildew) was inoculated to the plants by spraying. Then the plants were kept in a greenhouse for 7 to 10 days.

For evaluation, the diseased area ratio of each leaf was measured and the preventive value was calculated in accordance with the following formulae. The results are listed as "Preventive value 1" in Table 4. ##EQU1##

The compound numbers correspond to the compound Nos. in Tables 1, 2 and 3.

TEST EXAMPLE 2

Preventive activity on what brown rust

A wettable powder prepared in the same manner as described in Test Example 1 was diluted with water to a definite concentration and then applied by foliar application on wheat plants (var. Norin No. 61) at the 1 to 2 leaf stage grown in pots of 6 cm in diameter at a ratio of 10 ml/pot. After air-drying the chemical solution, a spore suspension of Puccinia recondita (a pathogen of wheat brown rust) was inoculated into the plants by spraying. Then the plants were kept in a moist chamber at 22° C. for 15 hours and then allowed to stand in a greenhouse for 7 days.

For evaluation, the diseased area ratio of each leaf was measured and the preventive value was calculated in accordance with the following formula. The results are listed as "Preventive value 2" in Table 4. ##EQU2##

The compound numbers correspond to the compound Nos. in Tables 1, 2 and 3.

                  TABLE 4                                                          ______________________________________                                         Compound                                                                               Active        Preventive Preventive                                    No.     ingredient (ppm)                                                                             value 1 (%)                                                                               value 2 (%)                                   ______________________________________                                          1      200           100        100                                            2      200           100        100                                            3      200           100        100                                            4      200            98         99                                            5      200            99        100                                            6      200            98         96                                            7      200            85         99                                            8      200            99         99                                            9      200            95         98                                           10      200            99        100                                           11      200           100         99                                           12      200            85         80                                           13      200            99         98                                           14      200           100        100                                           15      200            93         96                                           16      200           100         99                                           17      200           100        100                                           18      200           100        100                                           19      200           100        100                                           20      200           100        100                                           21      200           100        100                                           22      200            98         90                                           23      200           100         99                                           24      200           100        100                                           25      200           100        100                                           26      200            89         93                                           27      200           100        100                                           28      200           100        100                                           29      200           100         98                                           30      200            99         97                                           31      200           100        100                                           32      200           100        100                                           33      200           100        100                                           34      200           100        100                                           35      200           100        100                                           36      200            98         98                                           37      200           100        100                                           38      200           100        100                                           39      200           100        100                                           40      200           100        100                                           41      200           100        100                                           42      200           100        100                                           43      200           100        100                                           44      200           100        100                                           45      200           100        100                                           46      200           100        100                                           47      200           100        100                                           48      200           100        100                                           49      200           100        100                                           50      200           100        100                                           51      200           100        100                                           52      200           100        100                                           53      200           100        100                                           54      200           100        100                                           55      200           100        100                                           56      200           100        100                                           57      200           100        100                                           58      200           100        100                                           59      200           100        100                                           60      200           100        100                                           61      200           100        100                                           62      200           100        100                                           63      200           100        100                                           64      200           100        100                                           65      200           100        100                                           66      200           100        100                                           67      200           100        100                                           68      200            95         92                                           69      200            89         99                                           70      200            99         95                                           71      200           100        100                                           72      200            95         92                                           73      200            98         95                                           74      200           100        100                                           75      200           100        100                                           76      200           100        100                                           77      200           100        100                                           78      200            90         87                                           79      200           100        100                                           80      200           100        100                                           81      200           100        100                                           82      200            99         98                                           83      200           100        100                                           84      200            90         89                                           85      200            98         96                                           ______________________________________                                    

Residual activities were evaluated in cases simulating the practical uses as shown in following Test Examples. The tests were performed on the compounds according to the present invention as well as ones described in the prior arts, in order to clarify the advancement of the present invention over prior arts.

TEST EXAMPLE 3

Residual activity on wheat powdery mildew

A wettable powder prepared in the same manner as described in Formulation Example 1 was diluted with water to a definite concentration and then applied by foliar application to wheat plants (var. Norin No. 61) at the 1 to 2 leaf stage grown in pots of 6 cm in diameter at a ratio of 10 ml/pot. After keeping outdoor for 14 days, the plants were inoculated with a spore suspension of Erysiphe graminis (a pathogen of wheat powdery mildew) by spraying. Then the plants were allowed to stand in a greenhouse at 20° to 22° C. for 7 to 10 days.

For evaluation, the diseased area ratio of each leaf was measured and the preventive value was calculated in accordance with the following formula. The results are listed as "Preventive value 3" in Table 5. ##EQU3##

The compound numbers correspond to the compound Nos. in Tables 1, 2 and 3.

TEST EXAMPLE 4

Residual activity on wheat brown rust

A wettable powder prepared in the same manner as described in Test Example 1 was diluted with water to a definite concentration and then applied by foliar application to wheat plants (var. Norin No. 61) at the 1 to 2 leaf stage grown in pots of 6 cm in diameter at a ratio of 10 ml/pot. After keeping outdoor for 14 days, the plants were inoculated with a spore suspension of Puccinia recondita (a pathogen of wheat brown rust) by spraying. Then the plants were kept in a moist chamber at 22° C. for 24 hours and then allowed to stand in a greenhouse at 20° to 25° for 10 days.

For evaluation, the diseased area ratio of each leaf was measured and the preventive value was calculated in accordance with the following formula. The results are listed as "Preventive value 4" in Table 5. ##EQU4##

The compound numbers correspond to the compound No. in Tables 1, 2 and 3.

                                      TABLE 5                                      __________________________________________________________________________                        ##STR12##                                                                                     ##STR13##                                                                                     ##STR14##                                       250  50   10   250  50   10   250  50   10                   U  V              (ppm)          (ppm)          (ppm)                          __________________________________________________________________________     H  3-CF.sub.3 -                                                                        Preventive value 3                                                                       100  62   12   86    0   0    70    0   0                       Phenyl                                                                              Preventive value 4                                                                       100  77   23   68    0   0    98   13   0                            referential patent                                                                       invention compound                                                                            EP499823       W092/13830                             No.       No. 1                                                        CH.sub.3                                                                          Phenyl                                                                              Preventive value 3                                                                       100  88   59   99   48   0    99   55   0                            Preventive value 4                                                                       100  85   11   99   36   0    98   38   0                            referential patent                                                                       invention compound                                                                            EP499823       EP463488                               No.       No. 14                                                       CH.sub.3                                                                          4-Cl-                                                                               Preventive value 3                                                                       100  92   33   100  54   0    100  78   0                       Phenyl                                                                              Preventive value 4                                                                       100  97   27   95   31   0    100  83   0                            referential patent                                                                       invention compound                                                                            EP499823       EP463488                               No.       No. 17                                                       CH.sub.3                                                                          4-CH.sub.3 -                                                                        Preventive value 3                                                                       100  82   23   88    0   0    99   50   0                       Phenyl                                                                              Preventive value 4                                                                       100  58   18   53    0   0    98   45   0                            referential patent                                                                       invention compound                                                                            EP499823       EP463488                               No.       No. 28                                                       CH.sub.3                                                                          4-CF.sub.3 -                                                                        Preventive value 3                                                                       100  99   96   99    0    0   100  70   15                      Phenyl                                                                              Preventive value 4                                                                       100  96   91   99   24   0    99   77   28                           referential patent                                                                       invention compound                                                                            EP499823       EP463488                               No.       No. 24                                                       CH.sub.3                                                                          2-   Preventive value 3                                                                       100  99   95   85   20   0    92   77   0                       Naphthyl                                                                            Preventive value 4                                                                       100  95   92   92   48   0    90    0   0                            referential patent                                                                       invention compound                                                                            EP499823       EP463488                               No.       No. 76                                                       __________________________________________________________________________                                       ##STR15##                                                                     250  50   10                                                                   (ppm)                                         __________________________________________________________________________             Preventive value 3       52   8    0                                           Preventive value 4       16   0    0                                           referential patent       EP398692                                              No.                                                                    __________________________________________________________________________

Each of the compounds of the prevent invention is a novel one having an excellent fungicidal activity. It is particularly effective in controlling phytopathogenic fungi, which makes it highly useful as an agricultural/horticultural fungicide.

For example, these compounds exert high activity on rice blast (Pyricularia oryzae), rice sheath blight (Rhizoctonia solani) wheat powdery mildew (Erysiphe graminis f. sp. tritici) and barley powdery mildew (E, graminis f. sp. hodei), various leaf rusts of wheat and barley (e.g., Puccinia recondita), gray mold of vegetables and fruit trees (Botrytis cinerea) and late blight of various crops (Phytophthora infestance). Further, they have prolonged residual activity and excellent systemic action in plants, which makes them useful as an agricultural/horticultural fungicide.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. 

What is claimed is:
 1. A methoxyiminoacetic acid derivative represented by the following formula (I): ##STR16## wherein X represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; A represents a methylamino group; B represents --O--CR¹ R² --, wherein R¹ and R² independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group or a trifluoromethyl group, and Ar represents an optionally substituted aryl group or an optionally substituted heteroaryl group.
 2. The methoxyiminoacetic acid derivative as claimed in claim 1, wherein Ar representsan optionally substituted aryl group by 1 to 5 substituents which may be the same or different and, when the aryl group have 2 or more substituents, those adjacent to each other may be combined together to give a methylenedioxy or ethylenedioxy group and form a fused ring together with the aryl group, said substituents being selected from the group consisting of a cyano group; a halogen atom; an alkyl group having 1 to 6 carbon atoms; an alkenyl group having 2 to 4 carbon atoms optionally substituted by a halogen atom; a haloalkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 6 carbon atoms optionally substituted by a halogen atom or a cycloalkyl group having 3 to 6 carbon atoms; an alkylcarbonyloxy group having 1 to 7 carbon atoms optionally substituted by a halogen atom; an acylamino group having 1 to 7 carbon atoms optionally substituted by a halogen atom; an alkylthio group having 1 to 6 carbon atoms optionally substituted by a halogen atom; an aryl group optionally substituted by an alkyl group having 1 to 4 carbon atoms or a halogen atom; an aryloxy group optionally substituted by an alkyl group having 1 to 4 carbon atoms or a halogen atom; an alkylsulfonyloxy group having 1 to 6 carbon atoms optionally substituted by a halogen atom; an alkenyloxy group having 2 to 6 carbon atoms optionally substituted by a halogen atom; and an alkynyloxy group having 2 to 6 carbon atoms; or an optionally substituted heteroaryl group by 1 to 2 substituents which may be the same or different, said substituents being selected from the group consisting of a cyano group; a halogen atom; an alkyl group having 1 to 6 carbon atoms; a haloalkyl group having 1 to 4 carbon atoms; and an alkoxy group having 1 to 6 carbon atoms optionally substituted by a halogen atom; or a cycloalkyl group having 3 to 6 carbon atoms.
 3. An agricultural/horticultural fungicide containing a methoxyiminoacetic acid derivative as claimed in claim 2 as an active ingredient.
 4. An agricultural/horticultural fungicide containing a methoxyiminoacetic acid derivative as claimed in claim 1 as an active ingredient.
 5. A methoxyiminoacetic acid derivative represented by the following formula (II): ##STR17## wherein X represents a hydrogen atom or a halogen atom; R¹ and R² independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group or a trifluoromethyl group; and Ar represents an optionally substituted aryl group or an optionally substituted heteroaryl group.
 6. The methoxyiminoacetic acid derivative as claimed in claim 5, wherein X represents a hydrogen atom or a halogen atom; R¹ and R² independently represent a hydrogen atom, a cyano group or an alkyl group having 1 to 4 carbon atoms; and Ar representsan optionally substituted phenyl group or an optionally substituted naphthyl group, by one or more substituents being selected from the group consisting of a halogen atom; an alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms optionally substituted by a halogen atom; an acylamino group having 1 to 4 carbon atoms optionally substituted by a halogen atom; an alkylthio group having 1 to 3 carbon atoms; an alkylsulfonyloxy group having 1 to 3 carbon atoms optionally substituted by a halogen atom; or a trifluoromethyl group, or an optionally substituted thienyl group or an optionally substituted thiazolyl group, by one or more substituents selected from the group consisting of a halogen atom; an alkyl group having 1 to 4 carbon atoms; or a trifluoromethyl group.
 7. An agricultural/horticultural fungicide containing a methoxyiminoacetic acid derivative as claimed in claim 6 as an active ingredient.
 8. The methoxyiminoacetic acid derivative as claimed in claim 5, wherein X represents a hydrogen atom; R¹ represents a methyl group or a cyano group, and R² represents a hydrogen atom; and Ar represents a naphthyl group or an optionally substituted phenyl group by one or more substituents being selected from the group consisting of a halogen atom; an alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms optionally substituted by a halogen atom; an acylamino group having 1 to 4 carbon atoms optionally substituted by a halogen atom; an alkylsulfonyloxy group having 1 to 3 carbon atoms optionally substituted by a halogen atom; or a trifluoromethyl group.
 9. The methoxyiminoacetic acid derivative as claimed in claim 8, wherein Ar represents an optionally substituted phenyl group by one ore more substituents being selected from the group consisting of a halogen atom; an alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms optionally substituted by a fluorine, an alkylsulfonyloxy group having 1 to 3 carbon atoms optionally substituted by a fluorine; or a trifluoromethyl group.
 10. An agricultural/horticultural fungicide containing a methoxyiminoacetic acid derivative as claimed in claim 9 as an active ingredient.
 11. An agricultural/horticultural fungicide containing a methoxyiminoacetic acid derivative as claimed in claim 5 as an active ingredient.
 12. An agricultural/horticultural fungicide containing a methoxyiminoacetic acid derivative as claimed in claim 8 as an active ingredient.
 13. The methoxyiminoacetic acid as claimed in claim 8, wherein R¹ represents a methyl group.
 14. The methoxyiminoacetic acid as claimed in claim 13, wherein Ar represents a naphthyl group or a substituted phenyl group, the substituents being selected from the group consisting of one or two chlorines, trifluoromethyl, methyl and C₁ -C₂ alkoxy optionally substituted by two or three fluorine atoms.
 15. An agricultural or horticultural fungicide containing a methoxyiminoacetic acid derivative as claimed in claim 13 as an active ingredient.
 16. An agricultural or horticultural fungicide containing a methoxyiminoacetic acid derivative as claimed in claim 14 as an active ingredient.
 17. A method for controlling fungi, comprising the step of contacting the fungi or the materials, plants, seeds or soil threatened by fungal attack with a fungicidal amount of a compound as claimed in any one of claims 1-14. 